Purified alcohol sulphates and process of making the same



?atenite'd Mar. i939 pmrc Y sr rss PURIFIED ALCOHOL SULPHATES PROCESS OFMAKING THE SAME Hans Beller and John 3. Owen, Baton Rouge, La.

No Drawing.

Application September 23, 1936,

Serial No. 102,172 5 Claims. (61. 269-9912) The present inventionrelates to a method of purifying sulphated alcohol products, orsulphated olefine products obtainable from oleflnes described in U. S.Patent 1,965,962, or sulphated mixtures of such oleflnes and alcohols;for the purpose of manufacturing valuable assistants in the textile andrelated industries.

It has already been proposed to prepare such assistants by subjectingalcohols of high moleci ular weight, containing more than 10 carbonatoms in the molecule, or oleflnes, admixtures of oleflnes and alcoholsof similarv molecular weight range, to the-action of sulphonatingagents, such as concentrated sulphuric acid, iuming sulphuric i acid orchlorosulphonic acid, if desired in the presence of agents capable ofremoving water,

- such as acid anhydrides, for example, acetic anhydride, and/or ofinert diluents, such as carbontetrachloride, diethyl ether, and thelike. Val- 20 uable products are obtainedjin this way when the alcohols,or oleflnes, or mixtures of oleflnes and alcohols of similar molecularweight range which are subjected to the sulphonation are in acomparatively pure state; but if they are mixed with :5 other organicsubstances, and are not in a pure.

state, the resulting sulphates will be more or less impaired in theirvalue as assistants in the textile and related industries.

Such impure mixtures are obtained more par- 30 ticularly in the liquidphase oxidation of aliphatic hydrocarbons of high molecular weight, forexample, according to the process described in U. S.

Patent 1,909,295, issued May'l6, 1933. The liquid phase oxidationproducts usually consist of mix- 5 tures oi alcohols containing from to25 car-- bon atomswith non-oxidized initial hydrocarsons, and productsotherthan alcohols, produced by the same liquid phase oxidation, forexample, acids, esters, aldehydes, ketones, lactones, estos10 iides, andthe like. The sulphonation of the latter products is usually notperformed-as easily as that of the alcohols. Moreover, the productsobtained by the sulphonation of the substances other than alcoholsdo notexert the valuable prop- 45 erties offthe alcohol sulphonates. From atechnical pointof view it is rather difiicult to free the alcohols fromthe other non-saponifiable constituents; moreover, this purification canusually be performed only with a loss of alcohols.

50 We have now found that most valuable assistants in the textile andrelatedindustries, more particularly excellent wetting, washing,;anddetergingagents can be obtained by subjecting alcohols containing from10 to 25, preferably from 12 to 20, carbon atoms in their molecule, orole sion breaker.

fines, or mixtures of oleflnes and alcohols of similarmolecular weightrange, to the action of a sulphonating agent, if desired after removalof any acid, 1. e. saponiflable, constituents originally admixed withthe alcohols, neutralizing the prod- 5 ucts resulting from acidsulphonation by means of caustic alkalis, preferably by means ofconcentrated aqueous solutions of .caustic soda or potash, adding awater-soluble inorganic salt to the neutralized solution, and extractingthe lat- I0 I ter with an ether of less than 6 carbon atoms permolecule, thereby freeing the neutralized sulphonated products fromnon-sulphonated and non-sulphatable matter. The addition of awater-soluble inorganic salt to the neutralized solution serves to avoidtroublesome emulsions which would be formed during the subsequentextraction of the solution with an ether in the absence of suchinorganic salt. Such, salt acts as an emul- Ordinary extraction withether alone is therefore impractical. The extraction of r thesulphonated products may be performed with the addition of inorganic jsalts either before or after the'neutralization oi the sulphonationmixture. Thereby our process includes the 'extraction of acid esters,sulphonic acids and their salts from the crude sulphonation product..

The usual method of extracting the neutralized sulphonation product as,for instance, exemplified in U. S. Patent No. 1,993,375, issued March 5,1935, involves the use ofat least two volatile solvents, for example,gasoline fractions plus ethyl alcohol, or similar mixtures, and stillother solvents may be necessary in the sulphonation process proper, withcertain types of initial alcohols. The

present process purports to reduce the number of extraction solvents toone. This may be accomplished, ior instance,.by using ether as an inertdiluent during the sulphonation process and as an extraction agent inthe subsequent puriflcation step of the neutralized product in theparticular manner indicated below. v The said ethers suitable for;extraction come prise dimethyl ether, di-isopropyl ether, as well asmembers of the class of mixed, ethers, such as methyl ethyl ther, and soon. v The extraction is usually carried out at tem- .peratures betweenabout 0 ,C. and. the boiling point of the solvent used. Temperaturesrang-- ing between about 15 {3. and about 30 C. are, however, preferablyemployed for the extraction. l'i desired, the extraction maybe carriedout in a closed apparatus, in which case it is possible to workattemperatures above the boiling point of the extraction agent.

: by means of hydrogen,

88 as carbontetrachloride, or

The initial materials suitable for the sulphonation comprise, forexample, the alcohol containing mixtures obtainable for example,according to application Ser. No. 433,840, filed March 6,

1930, by catalytic reduction of hydrogenation of aliphaticmonocarboxylic acids and esters thereof, such as fatty oils, fats andwaxes, for example, esters of oleic, linoleic or train oil acids, cottonseed, sun'flower seed acids, and the like, as

'1 well as the free acids themselves, these hydro- 26 carbon atoms, suchas dodecyl, cetyl or oleyl alcohols.

The sulphonation of the alcohol containing mixtures which may beaccomplished by means of concentrated sulphuric acid, fuming sulphuric80 acid, and-more particularly chlorosulphonic acid,

may be carried out at temperatures between about 0 C. and about 30 C.,or with variations of the temperature during sulphation, if desired inthe presence of the aforesaid solvents, such diethyl ether, and/or ofWater-absorbing agents such as acetic acid anhydride, and usuallyproduces sulphuric esters of the initial alcohols, that is products inwhich one or more SOsH groups are connected to a in carbon atom by meansof an oxygen atom. Sulphonic acids may also result as products of thesulphonation. The neutralization of the said sulphuric esters orsulphonic acids is preferably carried out by incorporating thesulphonation :5 mixture with a concentrated aqueous solution of causticalkali or carbonates, or with organic bases such as triethanol amine orother suitable basic agents. The neutralized crude sulphonation productthus obtained is usually extracted with from 0.5 to 4, preferably with 1times its weight of the aforementioned extracting agents, thisextraction being repeated several times, but usually 3 or 4 extractionsare sufllcient for practically completely freeing the neutralizedsulpho- 5 nation product from all foreign substances. Sulphur trioxideis also a suitable sulphating agent.

The extraction may be carried out continuously by allowing the sulphatedmixture or the neutralized sulphated mixture each containing "a theproper concentration of dissolved inorganic salt, in water solution ormixed with water, to flow downwards through a tower packed with compactfiller bodies such as balls made from quartz, glass or other ceramicmaterials, etc., at which tower a current of said solvent is ledupwards. The resulting solution of the non-sulphonated andnon-sulphatable products is withdrawn at the top of the tower, while thesolution of pure sulphonates is drawn 0 oil at the bottom.

Mixers, settling tanks or other known methods for contmuous extractionare used in this step. Example 5 A total of 129 grams of distilled crudescale wax alcohols which were prepared from oxida-' tion products ofcrude scale wax by extraction and hydrogenation processes, are dissolvedin 129 cc. of petroleum ether solvent and sulphated at 19-22 C., usingthe theoretical amount of chlorosulphonic acid dissolved in 20 cc. 01'ethyl ether. After a total reaction period of 30 minutes, the sulphatedreaction mixture, is neutralized by cautiously pouring into sodiumhydroxide solution containing sumcient cracked ice to keep theneutralization temperature below C. To keep the proper pH value in thesolution during subsequent operations, 5 grams of crystallized trisodiumphosphate (NasPOa12HaO) dissolved in water, are added. A total of 770cc. of solution is obtained.

When cc. portions of the alkaline'sulphate solution are shakenvigorously with 30 cc. of diethyl ether, emulsions which break withextreme purified ether,- the emulsion breaks readily. Accordingly, 680cc. out of the total of 770 cc. of neutralized sulphation reactionmixture, corresponding to 114 grams of charge alcohols, in which 31grams of anhydrous sodium sulphate (NazSOo have been dissolved, areextracted four times with 250 cc. portions of the purified diethyl etherand filtered. The purified diethyl ether extracts are combined andwashed once with 200 cc. of water, to which 5 grams 01 anhydrous sodiumsulphate have been added in order to remove traces of alkyl sulphatedissolved in 'the ether. added to the which is further dried byspreading on a glass plate and allowing to stand at room temperature for88 hours under vacuum. I

The diethyl ether is removed from the 'unsulphated and unsulphatablematerial on a steam bath, the last traces being taken out with a streamof natural gas. A yield of 38% of unsulphated material (based on theweight of alcohols charged) is obtainedwhich has a hydroxyl number of '7and an acid number 01' 0.34. of the soap shows that the free fattymatter content has been reduced from 25% in the unextracted sulphatedproduct to 1.50% in the extracted soap. This value can readily be.reduced by increasing the numbers of extraction or the volume of diethylether used. I,

It is not intended to limit the type of alcohols to those used in theexample, since the present with the proper amount of water, obtainableby the sulphation of any non-aromatic type 01' alcohol.

It will be observed that the usual method oi extraction as shown, forinstance, in the aforementioned U. S. Patent No. 1,993,375, involvw theuse of at least two volatile solvents, and other solvents may benecessary in the sulp tion process with certain types of crude alcohols.The present process, therefore, reduces the number of solvent recoverysystems necessary in plant operation, to one.

Although diethyl ether is used in the present experiment, the use of anyother type of simple or mixed ethers or halogen substituted ethers ofeither type containing less than 6 carbon atoms per molecule is to becomprehendedin the scope of applicants claims. l

The wash water after filtration isa 49 carbon atoms,

bon atoms, olefines and mixtures of alcohols and olefines of similarmolecular weight range, to the action of a sulphonation agent,neutralizing the products resulting from such sulphonation by means ofan alkaline reacting substance, adding a water-solubleinorganic salt tothe neutralized solution, and extracting the latter with an ethercontaining less than 6 carbon atoms in its molecule, thereby freeing theneutralized sulphonated products from non-sulphonated andnon-sulphatable matter.

2. The process for the production and purification of products reactedwith sulphonating agents which comprises subjecting the liquid phaseoxidation products of normally liquid or solid nonaromatic hydrocarbonsselected from the group consisting of alcohols containing from 10 to 25carbon atoms, olefines and mixtures of olefines and alcohols of similarmolecular weight range, to the action of a sulphonating agent,neutralizing the products resulting from sulphonation, adding awater-soluble inorganic salt to the neutralized solution, and extractingthe latter with an ether of less than 6 carbon atoms per molecule,thereby freeing the neutralized sulphonated products fromnon-sulphonated and non-sulphatable matter.

3. The process for the production and'purification oi products reactedwith sulphonating agents which comprises subjecting the liquid phaseoxidation products of normally liquid or solid nonthe group aromatichydrocarbons selected from consisting of alcohols containing from 12 to20 olefines and mixtures of olefines and alcohols of similar molecularweight range, to the action of a sulphonating agent, neutralizing theproducts resulting from sulphonation by means of caustic alkalis addinga water-soluble inorganic salt to the neutralized solution, andextracting the latter with an ether of less than 6 carbon atoms permolecule, thereby freeing the' neutralized sulphonated products fromnon-sulphonated and non-sulphatable matter.

4. The process for the production and purification of products reactedwith sulphonating agents which comprises subjecting the liquid phaseoxidation products of normally liquid or solid nonaromatic hydrocarbonsselected from the group consisting of alcohols containing from 10 to 25carbon atoms, olefines and mixtures of olefines and alcohols of similarmolecular weight range, to the action of a sulphonating agent, adding awater-soluble inorganic salt to the neutralized solution, extracting thelatter with an ether of less than 6 carbon atoms per molecule, andneutralizing the sulphonation mixture.

5. The process for the production and purification of products reactedwith sulphonating agents which comprises subjecting a mixture ofalcohols obtainable from oxidation products of crude scale wax byextraction and hydrogenation, to the action of chlorosulphonic acid inethyl ether solution at a temperature of from 19-22 0., neutralizing thereaction mixture by pouring it into 10 per cent sodium carbonatesolution, care being taken that the neutralization temperature does notexceed 20 0., adding anhydrous sodium sulphate to the neutralizedsolution, and extracting the latter with diethyl ether, thereby freeingthe neutralized reaction mixture from non-sulphonatedand'non-sulphatable matter.

JOHN J. OWEN.

HANS BEULER. 4

